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NASA NTRS2018

Exoplanet Biosignatures: Understanding Oxygen as a Biosignature in the Context of Its Environment

Here we review how environmental context can be used to interpret whether O 2 is a biosignature in extrasolar planetary observations. This paper builds on the overview of current biosignature research discussed in Schwieterman et al. (2017), and provides an in-depth, interdisciplinary example of biosignature identification and observation that serves as a basis for the development of the general framework for biosignature assessment described in Catling et al., (2017). O 2 is a potentially strong biosignature that was originally thought to be an unambiguous indicator for life at high-abundance. In exploring O 2 as a biosignature, we describe the coevolution of life with the early Earth's environment, and how the interplay of sources and sinks in the planetary environment may have resulted in suppression of O 2 release into the atmosphere for several billion years, a false negative for biologically generated O 2 . False positives may also be possible, with recent research showing potential mechanisms in exoplanet environments that may generate relatively high abundances of atmospheric O 2 without a biosphere being present. These studies suggest that planetary characteristics that may enhance false negatives should be considered when selecting targets for biosignature searches. Similarly our ability to interpret O 2 observed in an exoplanetary atmosphere is also crucially dependent on environmental context to rule out false positive mechanisms. We describe future photometric, spectroscopic and time-dependent observations of O 2 and the planetary environment that could increase our confidence that any observed O 2 is a biosignature, and help discriminate it from potential false positives. The rich, interdisciplinary study of O 2 illustrates how a synthesis of our understanding of life's evolution and the early Earth, scientific computer modeling of star-planet interactions and predictive observations can enhance our understanding of biosignatures and guide and inform the development of next-generation planet detection and characterization missions. By observing and understanding O 2 in its planetary context we can increase our confidence in the remote detection of life, and provide a model for biosignature development for other proposed biosignatures.

Victoria S Meadows↗

NASA NTRSDate not supplied

On the Hunt for Detectable Biosignatures in Jezero Crater: What to Look for and Where

Introduction: The Perseverance rover, which is currently exploring Jezero crater on Mars, is equipped with seven instruments that allow for observation of textures, minerals, color, structure, and chemistry of rocks and sediments in order to search for signs of ancient life, understand the geologic history of the crater, and identify candidates for sample return (Farley et al. 2020). The first of these aims includes the direct detection of potential biosignatures, including textures, organic molecules, minerals, and elemental chemistries that are of biogenic origin (Mustard et al. 2013). The presence of these biosignatures will be constrained by the habitability of the local region, the preservation potential of the host rocks, and the sensitivity of the instrument suite, and their biogenicity will be investigated after return to Earth as part of the Mars Sample Return campaign. Here, we examine key targets on the three planned campaigns, potential biosignatures that may be present, and the capabilities of key rover instruments. High Potential Biosignature Sites in Jezero: To date, measurements have been made on multiple sites that both contain minerals known in terrestrial settings to preserve biosignatures and likely were habitable settings (Williford et al. 2021). Two examples include the fine-grained rocks at the base of the delta fan and the NW inner margin of the crater. Fine-grained Rocks at Base of Delta Fan. Fine-grained, clay-bearing rocks may have been deposited as muddy lake sediments that could have hosted life and preserved biosignatures settling out of the water column. The report of organic molecules by the Curiosity rover in the Sheepbed mudstone and Murray formation has highlighted this site in particular. Potential biosignatures in mudstones, especially those rich in silica (McMahon et al. 2018), microbialites and complex organics. NW Inner Margin of Crater. This unit, located along the inner margin of the crater, contains strong carbonate signatures and may have been the littoral zone of a lake (Horgan et al. 2020). The potential biosignatures here include microfossils, microbialites, biominerals, and complex organics. Detectability of Biosignatures by the Mars 2020 Instrument Suite: The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument comprises a Deep UV spectrometer, context imager, and color camera to generate spatially resolved chemical maps (Bhartia et al. 2020). It is sensitive to trace organics as well as a range of minerals and can detect native fluorescence from aromatic organics; the WATSON and ACI cameras can be used to observe morphologies such as stromatolitic laminations or filaments ranging from the tens of micron to millimeter scale. SHERLOC can detect organics that may be present in either of the high potential biosignature targets, as well as detect carbonates in the latter. However, the presence of high amounts of iron, such as in iron-rich clays, would cause attenuation of spectral response through UV absorption. The Planetary Instrument for X-ray Lithochemistry (PIXL) comprises an X-ray fluorescence spectrometer and camera that can scan rock surfaces to generate elemental maps (Allwood et al. 2020). PIXL can detect chemical biosignatures such as spatial variations of elemental abundances that may have resulted from biological activity. PIXL would be particularly useful in detecting fine textures and elemental chemistries in either high potential biosignature target, but cannot directly detect minerals such as carbonate. The SuperCam instrument performs three types of spectroscopy, color imaging, and acoustic recording to remotely examine elemental composition, minerals, organics, and textures (Maurice et al. 2021). Using laser induced breakdown spectroscopy and time resolved luminescence spectroscopy, SuperCam can detect major elemental building blocks of organics (i.e., C, H, N, O, P, S) and conjugated organic structures, respectively, which may be found in either site. While in other contexts, luminescence is a useful tool for biosignature identification, luminescence generated by the 532 nm laser may obscure the Raman signal. Conclusion: The three instruments discussed can be used collaboratively to establish the presence of potential biosignatures in samples. These high-priority samples may then be returned to Earth for detailed laboratory analysis.

S. Sharma↗

DOE OSTI2025

Multi-technique characterization of iron reduction by an Antarctic Shewanella : an analog system for putative Martian biosignature identification

ABSTRACT Microbes from terrestrial extreme environments enable testing of biosignature production in conditions relevant to astrobiological targets. Mars, which was likely more conducive to life during early warmer and wetter epochs, has inspired missions that search for signs of early life in the surficial rock record, including mineral or organic biosignatures. Microbial iron reduction is a common and ancient metabolism that may have also operated on other rocky celestial bodies. To investigate biosignature production during iron reduction, aShewanellasp. (strain BF02_Schw) isolated from a subglacial discharge known as Blood Falls, Antarctica, was incubated with the electron acceptor ferrihydrite (Fh). Biosignatures associated with Fh reduction were identified using a suite of techniques currently utilized or proposed for Mars missions, including X-ray diffraction and infrared, Mössbauer, and Raman spectroscopy. The biotic origin of features was validated by transcriptional changes observed between treatments with and without Fh and comparison to killed controls. In live treatments, Fh was reduced to magnetite and goethite, both detected in Martian lacustrine basins. Several soluble and volatile metabolites were also detected, including riboflavin and dimethyl sulfide (DMS), which could be astrobiological indicators of active microbial processes. While none of the identified biosignatures individually would serve as definitive proof of life (past or present), detecting concomitant features associated with known terrestrial biotic processes would provide compelling rationale for more targeted life detection missions. Terrestrial extremophiles can support the exploration of astrobiologically relevant microbial processes, validation of life detection instrumentation, and potentially the discovery of new biomarkers. IMPORTANCE Culture-based experiments with terrestrial extremophiles can elucidate biosignatures that may be analogous to those produced under extraterrestrial conditions, and thus inform sampling and technology strategies for future missions. Here, we demonstrate the production of several biosignatures under iron-reducing conditions byShewanellasp. BF02_Schw, originally isolated from an Antarctic analog feature. These biosignatures could be detectable using flight-ready instrumentation. Growth experiments with terrestrial extremophiles can identify biosignatures measurable by current methodologies and inform the development and optimization of techniques for detecting extant or extinct life on other worlds.

Biotechnology & Applied Microbiology↗

NASA NTRS2018

Exoplanet Biosignatures: At the Dawn of a New Era of Planetary Observations

The rapid rate of discoveries of exoplanets has expanded the scope of the science possible for the remote detection of life beyond Earth. The Exoplanet Biosignatures Workshop-Without-Walls (EBWWW) held in 2016 engaged the international scientific community across diverse scientific disciplines, to assess the state of the science and technology in the search for life on exoplanets, and to identify paths for progress. The workshop activities resulted in five (5) major review papers which provide: 1) an encyclopedic review of known and proposed biosignatures and models used to ascertain them; 2) an in-depth review of O2 as a biosignature, rigorously examining the nuances of false positives and negatives for evidence of life; 3) a Bayesian framework to comprehensively organize current understanding to quantify confidence in biosignature assessments; 4) an extension of that Bayesian framework in anticipation of increasing planetary data and novel concepts of biosignatures, and 5) a review of the upcoming telescope capabilities to characterize exoplanets and their environment. Because of the immense content of these review papers, this summary provides a guide to their complementary scope and highlights salient features. Strong themes that emerged from the workshop were that biosignatures must be interpreted in the context of their environment, and that frameworks must be developed to link diverse forms of scientific understanding of that context to quantify the likelihood that a biosignature has been observed. Models are needed to explore the parameter space where measurements will be widespread but sparse in detail. Given the technological prospects for large ground-based telescopes and direct imaging from space-based observatories, the detection of atmospheric signatures of a few potentially habitable planets may come before 2030.

spectral imaging↗

NASA NTRS2017

NExSS/NAI Joint ExoPAG SAG 16 Report on Remote Biosignatures for Exoplanets

Future exoplanet observations will soon focus on the search for life beyond the Solar System. Exoplanet biosignatures to be sought are those with global, potentially detectable, impacts on a planet. Biosignatures occur in an environmental context in which geological, atmospheric, and stellar processes and interactions may work to enhance, suppress or mimic these biosignatures. Thus biosignature scienceis inherently interdisciplinary. Its advance is necessary to inform the design of the next flagship missions that will obtain spectra of habitable extrasolar planets. The NExSS NAI Joint Exoplanet Biosignatures Workshop Without Walls brought together the astrobiology, exoplanet, and mission concept communities to review, discuss, debate, and advance the science of remote detection of planetary biosignatures. The multi-meeting workshop began in June 2016, and was a process that engaged a broad range of experts across the interdisciplinary reaches of NASA's Nexus for Exoplanet System Science (NExSS) program, the NASA Astrobiology Institute (NAI), NASAs Exoplanet Exploration Program (ExEP), and international partners, such as the European Astrobiology Network Association (EANA) and Japans Earth Life Science Institute (ELSI). These groups spanned expertise in astronomy, planetary science, Earth sciences, heliophysics, biology, instrument mission development, and engineering.

Kiang, Nancy Y.↗

NASA NTRS2018

Seeking the Signs of Life: Assessing the Presence of Biosignatures in the Returned Sample Suite

A biosignature (''definitive biosignature'' or DBS) is an object, substance and/or pattern whose origin specifically requires a biological agent. One category of DBS are complex organic molecules and/or structures whose formation and abundances relative to other compounds are virtually unachievable in the absence of life. A potential biosignature (PBS) is an object, substance and/or pattern that might have a biological origin and thus compels investigators to gather more data before reaching a conclusion as to the presence or absence of life. The usefulness of a PBS is determined not only by the probability that life created it but also by the improbability that nonbiological processes produced it. Because habitable planetary environments create nonbiological features that can mimic biosignatures, these environments must be characterized to the extent necessary to provide a context that is essential for confirming the presence of DBS. Environmental conditions also must have allowed biosignatures to be preserved and amenable to detection. Categories of biosignatures and their measurement requirements are indicated below.

Source record↗

NASA NTRS2018

Exoplanet Biosignatures: A Review of Remotely Detectable Signs of Life

In the coming years and decades, advanced space- and ground-based observatories will allow an unprecedented opportunity to probe the atmospheres and surfaces of potentially habitable exoplanets for signatures of life. Life on Earth, through its gaseous products and reflectance and scattering properties, has left its fingerprint on the spectrum of our planet. Aided by the universality of the laws of physics and chemistry, we turn to Earth's biosphere, both in the present and through geologic time, for analog signatures that will aid in the search for life elsewhere. Considering the insights gained from modern and ancient Earth, and the broader array of hypothetical exoplanet possibilities, we have compiled a comprehensive overview of our current understanding of potential exoplanet biosignatures, including gaseous, surface, and temporal biosignatures. We additionally survey biogenic spectral features that are well known in the specialist literature but have not yet been robustly vetted in the context of exoplanet biosignatures. We briefly review advances in assessing biosignature plausibility, including novel methods for determining chemical disequilibrium from remotely obtainable data and assessment tools for determining the minimum biomass required to maintain short-lived biogenic gases as atmospheric signatures. We focus particularly on advances made since the seminal review by Des Marais et al. The purpose of this work is not to propose new biosignature strategies, a goal left to companion articles in this series, but to review the current literature, draw meaningful connections between seemingly disparate areas, and clear the way for a path forward.

biosignatures↗

NASA NTRS2024

Detectability Simulations of a Near-infrared Surface Biosignature on Proxima Centauri b with Future Space Observatories

Telescope missions are currently being designed that will make direct imaging of habitable exoplanets possible in the near future, and studies are needed to quantify the detectability of biosignature features in the planet's reflectance spectrum. We simulated the detectability of a near-infrared-absorbing surface biosignature feature with simulated observations of the nearby exoplanet Proxima Centauri b. We modeled a biosignature spectral feature with a reflectance spectrum based on an anoxygenic photosynthetic bacterial species that has strong absorption at 1 μm, which could make it well suited for life on an M-dwarf-hosted planet. We modeled the distribution of this organism across the planet's surface based on climate states from a 3D general circulation model (GCM) that were Archean- and Proterozoic-like exo-Earth analogs. We included the GCM states' prognostically simulated water clouds and added organic haze into the Archean-like atmospheres. We simulated observations of these Proxima Centauri b scenarios with the LUVOIR-A and B telescope concepts, with LUVOIR-B serving as a proxy to the planned Habitable Worlds Observatory. We calculated the integration times necessary to detect the biosignature and found that it would be detectable on Proxima Centauri b if the organism is moderately abundant (greater than a 1%–4% global surface area coverage), as long as the atmosphere is transmitting in the wavelength range under consideration. Small amounts of methane, clouds, and haze do not greatly impede detectability. We found preliminary evidence that such a biosignature would be detectable on exoplanets within 15 pc, but further investigations are needed to corroborate this.

Exoplanet astronomy↗

NASA NTRS2013

Mars Biosignature - Detection Capabilities: A Method for Objective Comparison of In Situ Measurements and Sample Return

A Mars sample-return mission has been proposed within NASA's Mars Exploration Program. Studying Martian samples in laboratories on Earth could address many important issues in planetary science, but arguably none is as scientifically compelling as the question of whether biosignatures indicative of past or present life exist on that planet. It is reasonable to ask before embarking on a sample-return mission whether equivalent investigation of Martian biosignatures could be conducted in situ. This study presents an approach to (1)identifying an optimal instrument suite for in situ detection of biosignatures on Mars,and (2)comparing the projected confidence level of in situ detection in a 2026 timeframe to that of Earth-based analysis. We identify a set of candidate instruments, the development of which is projected to be achievable by 2026 well within a $200 million cost cap. Assuming that any biosignatures near the surface of Mars are similar to those of terrestrial life, we find that this instrument suite, if successfully developed and deployed, would enable in situ biosignature detection at essentially the same level of confidence as that of Earth-based analysis of the same samples. At a cost cap of half that amount,the confidence level of in situbiosignature detection analysis could reach about 90% that of Earth-based investigations.

National Environmental Policy Act (NEPA)↗

NASA NTRS2018

Biosignature Anisotropy Modeled on Temperate Tidally Locked M-Dwarf Planets

A planet’s atmospheric constituents (e.g., O2, O3, H2Ov, CO2, CH4, and N2O) can provide clues to its surface habitability, and may offer biosignature targets for remote life detection efforts. The plethora of rocky exoplanets found by recent transit surveys (e.g., the Kepler mission) indicates that potentially habitable systems orbiting K- and M-dwarf stars may have very different orbital and atmospheric characteristics than Earth. To assess the physical distribution and observational prospects of various biosignatures and habitability indicators, it is important to understand how they may change under different astrophysical and geophysical configurations, and to simulate these changes with models that include feedbacks between different subsystems of a planet’s climate. Here we use a three-dimensional (3D) Chemistry–Climate model (CCM) to study the effects of changes in stellar spectral energy distribution (SED), stellar activity, and planetary rotation on Earth analogs and tidally locked planets. Our simulations show that, apart from shifts in stellar SEDs and UV radiation, changes in illumination geometry and rotation-induced circulation can influence the global distribution of atmospheric biosignatures. We find that the stratospheric day-to-nightside mixing ratio differences on tidally locked planets remain low (<20%) across the majority of the canonical biosignatures. Interestingly, however, secondary photosynthetic biosignatures (e.g., C2H6S) show much greater (∼67%) day-to-nightside differences, and point to regimes in which tidal locking could have observationally distinguishable effects on phase curve, transit, and secondary eclipse measurements. Overall, this work highlights the potential and promise for 3D CCMs to study the atmospheric properties and habitability of terrestrial worlds.

Chen, Howard↗

NASA NTRS2019

Biosignatures of Past Life are Also Relevant to the Search for Extant Life

A biosignature (a “definitive biosignature” or DBS) is an object, substance pattern and/or process whose origin requires a biological agent. A potential biosignature (PBS) is a feature that might have a biological origin and thus compels investigators to gather more data before determining the presence or absence of life. The usefulness of a PBS is determined not only by the probability that life created it but also by the improbability that nonbiological processes produced it. Habitable planetary environments create nonbiological features that can mimic biosignatures, so these environments must be characterized to the extent necessary to confirm the presence of DBS. Environments also must have allowed biosignatures to be preserved and to remain amenable to detection.

Des Marais, D. J.↗

NASA NTRS2017

Biosignatures in the Context of Low Energy Flux

Many of the features that are thought of as biosignatures - including the mediation of chemical and physical processes with speed, specificity, and selectivity - result directly or indirectly from life's unique capability to mediate and direct energy flux. As such, it is important to consider the impact that differences in energy flux may have on the quantity and quality of evidence for life. Earth differs from every other body in our solar system in the magnitude of biologically-usable energy flux into a liquid water environment. On a global basis, the capture of light energy into photosynthesis and the flux of chemical energy represented in the products of that photosynthesis (organic material + O2) are about six and four orders of magnitude larger, respectively, than the flux of energy represented in geochemical sources. Our conception of what an inhabited world "looks like" and our intuition about how to search for life are based in this high-energy context. Energy fluxes on worlds beyond Earth may be better approximated by the million-fold smaller flux provided to Earth's biosphere by geochemical sources. As a result, the nature, abundance, and quality of evidence for life that could be expected on an inhabited extraterrestrial world within our solar system may differ profoundly from that found on Earth. Understanding this potential difference in quantitative terms provides important context for the formulation of life detection strategies. The influence of energy flux on biosignatures can be evaluated through reference to the two basic purposes into which life partitions energy flux: (1) Life expends energy to sustain existing biomass in a metabolic steady state (metabolically functional but non-growing). The formal representation of this relationship in the traditional microbiology literature equates biomass directly with energy flux. The direct implication is that worlds having lower energy flux will have correspondingly lower potential to support biomass. Life detection strategies that directly target extant organisms should therefore be prepared to encounter average biomass densities that may be many orders of magnitude smaller than those found in most of Earth's surface environments (2) Life expends energy to synthesize new biomass. An end-member case in which new biomass is created at the energy-limited rate and the corresponding cells are immediately destroyed (so that the energy partitioned to cell maintenance is minimized) establishes an upper bound on the rate at which biological material can enter a bulk global pool. For a specified bulk concentration [i] of any particular biological compound, i, or for biologically produced matter overall, this synthesis rate, R (sub i), defines a characteristic time scale tau (sub i) equals [i] divided by R (sub i). tau (sub i) can be thought of as (a) the minimum time required for biosynthesis to yield a specific bulk concentration (e.g., a detection threshold) of i, and (b) the average residence time of i within a bulk pool when [i] is held in steady state through a balance between biosynthesis and attrition by physical, chemical, or biological consumption. tau (sub i) becomes an important quantity in considering the potential utility of enantiomeric excess (as a product of homochiral biosynthesis) as a biosignature. Spontaneous racemization of amino acids acts to "erase" the signature of homochiral synthesis over time scales that may range from hundreds to hundreds of thousands of years, depending on temperature. For environments in which low energy flux translates to low rates of biosynthesis, including the synthesis of homochiral amino acids, amino acid residence times in pools having detectable concentrations may compare to or significantly exceed the time scale for racemization. This and similar consequences of long residence times should be considered in the formulation of life detection strategies based on detection of biologically-produced species. Fluxes of biologically-useful energy on potentially habitable worlds within our solar system are, at present, not well constrained. Improving such constraint has the potential to inform priorities in the formulation and targeting of search-for-life strategies, based on the implications of energy flux for the abundance and quality of biosignatures overall, and in specific categories.

ENERGY FLUX↗

NASA NTRS2020

Preservation of Organic Carbon in Dolomitized Cambrian Stromatolites and Implications for Microbial Biosignatures in Diagenetically Replaced Carbonate Rock

Stromatolites have been a major focus in the search for ancient microbial life, however, the organic carbon biosignatures of dolomitized stromatolites have not yet been fully characterized or correlated with their dolomitizing conditions. Although dolomitization rarely preserves microbial morphology, the presence of organic carbon can provide valuable information for characterization of fossils’ biogenicity, syngenicity, and indigeneity to their host rock. The Cambrian Allentown Formation in New Jersey, USA, is an excellent example of dolomitized stromatolites and thrombolites containing diagenetically modified microbial biosignatures. Based on XRD and EPMA data, the dolomite composition is typically stoichiometric, with varying degrees of cationic ordering. The outcrop underwent early dolomitization in a marginal-marine setting and later burial diagenesis resulting in multi-generational dolomite formation: (1) 2 microspar dolomite formed by early diagenetic replacement at or near the surface, (2) zoned dolomite formed penecontemporaneously with the microspar phase as rhombohedral crystals by infilling primary pore spaces within the microspar matrix. The rhombic crystals continued to grow outward in alternating stages of Fe-enriched and -depleted fluids, which were preserved in zoned rims and revealed by cathodoluminescence, and (3) saddle dolomite formed during late stage deep burial with Fe- and Mn-rich fluids, and occurs as a void-filling, high-temperature phase. Organic carbon, characterized using confocal Raman microscopy, has an exclusive distribution within the microspar dolomite, and the D and G bands’ characteristics reveal similar thermal alteration to the host rock, indicating that the mapped organic carbon is indigenous and syngenetic with the Cambrian carbonates. The findings presented in this study reveal organic matter found within microspar of various dolomitized facies deriving from different source pools of organic carbon. This study sheds light on biosignatures in secondary dolostones and may aid biosignature detection in older carbonate rocks on Earth and Mars.

Dolomitization↗

NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system has been guided by our under-standing of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure, and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-excesses of chiral amino acids or sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. However, studies of primitive meteorites have revealed that they contain extraterrestrial amino acids and sugar acids with large enantiomeric excesses (60% and higher) that resulted from non-biological processes [1], complicating the use of chiral asymmetry by itself as a definitive biosignature. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, is an objective of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite on Mars [2-5], NASA’s Curiosity rover has found evidence of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars [5], indigenous achiral amino acids have been identified in one martian meteorite [6]. It is expected that amino acid racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [7]. The ESA/Roscosmos ExoMars mission scheduled for launch next year includes the Rosalind Franklin rover designed to acquire samples from a depth of ~2 m and deliver them to a suite of instruments, including the Mars Organic Molecule Analyzer (MOMA). The MOMA instrument contains a wet chemistry experiment designed specifically for the detection of amino acids and measurement of their enantiomeric compositions [8]. The complexity and limited duration of spaceflight operations, and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic com-pounds in ancient rocks, make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, bulk and molecule-specific isotopic, and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars derives from bio-tic or abiotic processes. Ultimately, Mars Sample Return of rock cores collected by NASA’s Perseverance rover may be our best chance of identifying chemical biosignatures, including any chiral amino acid asymmetry resulting from a past or present martian biota, if one ever existed on Mars. Here we review our current knowledge of the distributions, and enantiomeric and isotopic com-positions of amino acids found in meteorites compared to terrestrial biochemistry. We also propose a set of measurement criteria that should be used to help establish the sources of any amino acids detected in samples returned from Mars using state-of-the-art gas and liquid chromatography mass spectrometry techniques [1].

D P Glavin↗

NASA NTRSDate not supplied

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗

NASA NTRSDate not supplied

Interpretable Machine Learning Models for Autonomous Characterization of Analogue Ocean World Seawater Chemistry and Biosignature Potential Using Isotope Ratio Data

Background: Future missions to ocean worlds, such as Enceladus and Europa, will attempt to characterize the subsurface seawater chemistry and assess the potential for life. Such missions will be equipped with capabilities to precisely measure volatile isotopes in plumes, atmospheres, and exospheres. Motivation: While large isotopic fractionations can indicate a biological source, there are signatures resulting from abiotic geochemical processes that mimic isotopic biosignatures. While machine learning (ML) has the potential to disentangle competing effects and biotic mimicry, high-dimensional isotope ratio mass spectrometry (IRMS) data is likely to contain noise/irrelevant features and involve complex statistical interactions that make human inference and interpretation difficult. Further, ML predictions with as far-reaching implications as an extraterrestrial biosignature on an ocean world requires the use of interpretable models (i.e., not “black box” models) with physically and mathematically meaningful feature spaces along with false positive diagnostics. Methods: We use volatile CO2 IRMS data of analogue ocean world seawaters to validate an ML approach to provide biogeochemical context for biosignature detection. We employ a feature selection method called nearest-neighbor projected distance regression (NPDR) that detects statistical interactions and helps elucidate the mechanisms of the Random Forest classification models. Results: We train and validate predictive ML models on volatile CO2 IRMS data of analogue ocean world seawaters to predict major salt components (e.g., MgSO4, NaHCO3), pH, ionic strength, and the presence of biosignatures. Features derived from IRMS measurements are augmented with extracted time-series features. Our results show high test accuracy and interpretability, which is increased by interaction network visualization, sample-wise variable importance scores, and single-sample class probability estimates. We demonstrate an ML mission software solution that triggers autonomous data transmission and biogeochemical sample prediction.

geochemistry↗

NASA NTRS2024

Interpretable Machine Learning for Molecular Biosignatures: a Novel Single-Sample Feature Importance Method That Is Sensitive To Statistical Interactions

Isotope ratio mass spectrometry (IRMS) of volatiles (e.g., CO 2 ) promises to be a powerful tool for potential biosignature detection for future missions to ocean worlds (OW) such as Europa and Enceladus. Machine learning (ML) methods for IRMS data could enable science autonomy by onboard prediction of seawater chemistry and biosignature presence. However, ML models are likely to be complex and involve statistical interactions between features (variables), which can make predictions seem opaque and enigmatic. For ML predictions as significant as extraterrestrial biosignatures, we must place extraordinary confidence in models. It is therefore essential that these models make interpretable predictions (i.e., human-understandable) and include false-prediction diagnostics. We achieve high accuracy and interpretability in ML biosignature and seawater chemistry models for OW through a nearest-neighbors feature selection tool that detects statistical interactions between predictors, constructs interaction networks for visualization of selected features working together to make a prediction, and reports single-sample feature importance scores for false-detection diagnostics. Here we develop a novel single-sample nearest-neighbors projected distance regression(ssNPDR) feature selection method that improves upon existing single-sample algorithms through the inclusion of statistical interactions while providing false-prediction diagnostics for ML models.

geochemistry↗

NASA NTRSDate not supplied

Algorithmic Classification of Raman Spectra Biosignatures: Improving Life Detection Confidence

“Agnostic” biosignatures – indicators of life (or the absence of life), independent of a particular biochemistry – are increasingly considered a high standard for life detection. The Ladder of Life Detection (2018) called for investigating how combinations of independent and different potential biosignatures affect confidence. To address this gap, statistical classification of elemental abundances, isotopic fractionation, and reflectance spectroscopy (VNIR) has been implemented. Raman spectroscopy, highly desirable due to its wide availability, has the potential to improve this predictive power. This work implemented biosignature classification algorithms on Raman data alone, in preparation for combination with the other data types. Raman spectroscopy data was collected from published databases and papers as part of a manually curated dataset of “indicative” and “non-indicative of life” samples. These currently include 61 non-indicative samples (meteorites, magnetite); 3 indicative living samples (bacteria); 20 indicative non-living samples (chalk, bone); and 12 indicative mixed (with non-indicative material) samples (soil, microbial mats). Laboratory work is ongoing to characterize additional samples, particularly a greater breadth of mixed systems. Spectra were interpolated, filtered with the Savitzsky-Golay filter, and de-noised. For a preliminary examination, agnostic features were manually extracted including mean intensity, number of peaks, and mean peak width. Different peak prominences and filtering polynomials were used to refine features. Classification algorithms were implemented: k-nearest neighbors (KNN), logistic regression (LR), linear support vector machines (SVM), random forest (RF), Gaussian naïve bayes (GNB). Lastly, Monte Carlo simulations on 1,000 50%-train-test-splits were used to validate classification performance and feature significance. The preliminary feature set achieved its highest AUC of 0.52 with LR, with no strongly discriminatory features. Work to improve feature extraction, such as through deep learning with back propagation, is planned. In future work, the Raman data will be combined with the other data types, and potentially new data types such as enantiomeric excess. This project was partially supported through the NASA Ames Project EXcellence (APEX) incubator program.

Astrobiology↗